Development and characterization of polylactic acid/starch biocomposites - From melt blending to preliminary life cycle assessment.

This study presents a comprehensive analysis encompassing melt blending, characterization, life cycle assessment (LCA), and 3D printing of a range of polylactic acid (PLA)/starch biocomposites, with starch content varying from 0 to 50 wt%. To enhance compatibility between the starch particles and the PLA matrix, we utilized a solvent-free method to graft N-octadecyl isocyanate (ODI) molecules onto the surface of the starch particles, resulting in ODI-g-starch, which yielded several improved properties. Notably, toughness and elongation at break improved by approximately 170 % and 300 %, respectively. Moreover, the crystallinity increased from 11.6 % in plain PLA to 30.1 %, suggesting that the uniform dispersion of ODI-g-starch particles acted as nucleating sites for the crystallization of PLA chains. Additionally, viscosity decreased significantly with the introduction of ODI-g-starch particles, indicating their plasticizing effect, thereby enhancing the processability and ease of fabrication of the biocomposite. Crucially, our LCA analysis revealed a significant reduction in the carbon footprint of these biocomposites, up to 18 % and 63 %, compared to plain PLA and selected fossil-based plastics, respectively, upon the incorporation of ODI-g-starch. In summary, our research introduces the newly developed PLA/starch biocomposites as a sustainable and eco-friendly alternative to commercially available plain PLA and specific fossil-based plastics.

Variable-transmittance bio-based phase change composites based on the photothermal property of pectin.

In this study, the possibility of using a natural polysaccharide, pectin, in a novel function as a photothermal material was investigated by fabricating a Pectin/Polyethylene glycol (PEG)/Poly(methyl methacrylate) (PMMA) composite via the infiltration of PEG/PMMA polymer mixture into freeze-casted pectin cryogel template. The Pectin/PEG/PMMA composite has high latent heat of 48 J/g, excellent UV blocking ability, and tailorable transmittance as well as capacity to energy storage via photothermal heating to the melting point of PEG under sunlight. The photothermal effect can be enhanced with the increase of pectin concentration and irradiation intensity. Furthermore, by using the Pectin/PEG/PMMA composite as a window of a model house could effectively reduce the temperature rise inside the house under irradiation and reduce the temperature drop after turning off the irradiation, as compared to a model house with conventional glass as the window material. Therefore, this work provides a new application of pectin as photothermal material and opens the opportunity to develop novel sustainable bio-based photothermal materials.

Anisotropic Superhydrophobic Properties Replicated from Leek Leaves.

A bio-inspired approach to fabricate robust superhydrophobic (SHB) surfaces with anisotropic properties replicated from a leek leaf is presented. The polydimethylsiloxane (PDMS) replica surfaces exhibit anisotropic wetting, anti-icing, and light scattering properties due to microgrooves replicated from leek leaves. Superhydrophobicity is achieved by a novel modified candle soot (CS) coating that mimics leek's epicuticular wax. The resulting surfaces show a contact angle (CA) difference of ≈30° in the directions perpendicular and parallel to the grooves, which is similar to the anisotropic properties of the original leek leaf. The coated replica is durable, withstanding cyclic bending tests (up to 10 000 cycles) and mechanical sand abrasion (up to 60 g of sand). The coated replica shows low ice adhesion (10 kPa) after the first cycle; and then, increases to ≈70 kPa after ten icing-shearing cycles; while, anisotropy in ice adhesion becomes more evident with more cycles. In addition, the candle soot-coated positive replica (CS-coated PR) demonstrates a transmittance of ≈73% and a haze of ≈65% at the wavelength of 550 nm. The results show that the properties depend on the replicated surface features of the leek leaf, which means that the leek leaf appears to be a highly useful template for bioinspired surfaces.

Light-Driven Multidirectional Bending in Artificial Muscles.

Using light to drive polymer actuators can enable spatially selective complex motions, offering a wealth of opportunities for wireless control of soft robotics and active textiles. Here, the integration of photothermal components is reported into shape memory polymer actuators. The fabricated twist-coiled artificial muscles show on-command multidirectional bending, which can be controlled by both the illumination intensity, as well as the chirality, of the prepared artificial muscles. Importantly, the direction in which these artificial muscles bend does not depend on intrinsic material characteristics. Instead, this directionality is achieved by localized untwisting of the actuator, driven by selective irradiation. The reaction times of this bending system are significantly - at least two orders of magnitude - faster than heliotropic biological systems, with a response time up to one second. The programmability of the artificial muscles is further demonstrated for selective, reversible, and sustained actuation when integrated in butterfly-shaped textiles, along with the capacity to autonomously orient toward a light source. This functionality is maintained even on a rotating platform, with angular velocities of 6°/s, independent of the rotation direction. These attributes collectively represent a breakthrough in the field of artificial muscles, intended to adaptive shape-changing soft systems and biomimetic technologies.

A Stable Perovskite Sensitized Photonic Crystal P-N Junction with Enhanced Photoelectrochemical Hydrogen Production.

The slow photon effect in inverse opal photonic crystals represents a promising approach to manipulate the interactions between light and matter through the design of material structures. This study introduces a novel ordered inverse opal photonic crystal (IOPC) sensitized with perovskite quantum dots (PQDs), demonstrating its efficacy for efficient visible-light-driven H2 generation via water splitting. The rational structural design contributes to enhanced light harvesting. The sensitization of the IOPC with PQDs improves optical response performance and enhances photocatalytic H2 generation under visible light irradiation compared to the IOPC alone. The designed photoanode exhibits a photocurrent density of 3.42 mA cm-2 at 1.23 V vs RHE. This work advances the rational design of visible light-responsive photocatalytic heterostructure materials based on wide band gap metal oxides for photoelectrochemical applications.

Processing factors affecting roughness, optical and mechanical properties of nanocellulose films for optoelectronics.

This work aims to understand how nanocellulose (NC) processing can modify the key characteristics of NC films to align with the main requirements for high-performance optoelectronics. The performance of these devices relies heavily on the light transmittance of the substrate, which serves as a mechanical support and optimizes light interactions with the photoactive component. Critical variables that determine the optical and mechanical properties of the films include the morphology of cellulose nanofibrils (CNF), as well as the concentration and turbidity of the respective aqueous suspensions. This study demonstrates that achieving high transparency was possible by reducing the grammage and adjusting the drying temperature through hot pressing. Furthermore, the use of modified CNF, specifically carboxylated CNF, resulted in more transparent films due to a higher nanosized fraction and lower turbidity. The mechanical properties of the films depended on their structure, homogeneity (spatial uniformity of local grammage), and electrokinetic factors, such as the presence of electrostatic charges on CNF. Additionally, we investigated the angle-dependent transmittance of the CNF films, since solar devices usually operate under indirect light. This work demonstrates the importance of a systematic approach to the optimization of cellulose films, providing valuable insight into the optoelectronic field.

Heat-Induced Actuator Fibers: Starch-Containing Biopolyamide Composites for Functional Textiles.

This study introduces the development of a thermally responsive shape-morphing fabric using low-melting-point polyamide shape memory actuators. To facilitate the blending of biomaterials, we report the synthesis and characterization of a biopolyamide with a relatively low melting point. Additionally, we present a straightforward and solvent-free method for the compatibilization of starch particles with the synthesized biopolyamide, aiming to enhance the sustainability of polyamide and customize the actuation temperature. Subsequently, homogeneous dispersion of up to 70 wt % compatibilized starch particles into the matrix is achieved. The resulting composites exhibit excellent mechanical properties comparable to those reported for soft and tough materials, making them well suited for textile integration. Furthermore, cyclic thermomechanical tests were conducted to evaluate the shape memory and shape recovery of both plain polyamide and composites. The results confirmed their remarkable shape recovery properties. To demonstrate the potential application of biocomposites in textiles, a heat-responsive fabric was created using thermoresponsive shape memory polymer actuators composed of a biocomposite containing 50 wt % compatibilized starch. This fabric demonstrates the ability to repeatedly undergo significant heat-induced deformations by opening and closing pores, thereby exposing hidden functionalities through heat stimulation. This innovative approach provides a convenient pathway for designing heat-responsive textiles, adding value to state-of-the-art smart textiles.

In-situ Monitoring of Photocontrollable Wrinkle Erasure in Azobenzene-based Supramolecular Systems.

In this contribution, dynamic photoinduced wrinkle erasure enabled by photomechanical changes in supramolecular polymer-azo complexes was characterized via confocal microscopy. Different photoactive molecules, disperse yellow 7 (DY7) and 4,4'-dihydroxyazobenzene (DHAB), were compared to 4-hydroxy-4'-dimethylaminoazobenzene (OH-azo-DMA). The characteristic erasure times of wrinkles were quickly assessed by using an image processing algorithm. The results confirm that the photoinduced movement on the topmost layer can be successfully transferred to the substrate. Furthermore, the chosen supramolecular strategy allows decoupling the effect of molecular weight of the polymer and photochemistry of the chromophore, allowing quantitative comparison of wrinkling erasure efficiency of different materials and providing a facile way to optimize the system for specific applications.

Active Textile Fabrics from Weaving Liquid Crystalline Elastomer Filaments.

Active fabrics, responding autonomously to environmental changes, are the "Holy Grail" of the development of smart textiles. Liquid crystal elastomers (LCEs) promise to be the base materials for large-stroke reversible actuation. The mechanical behavior of LCEs matches almost exactly the human muscle. Yet, it has not been possible to produce filaments from LCEs that will be suitable for standard textile production methods, such as weaving. Based on the recent development of LCE fibers, here, the crafting of active fabrics incorporating LCE yarn, woven on a standard loom, giving control over the weave density and structure, is presented. Two types of LCE yarns (soft and stiff) and their incorporation into several weaving patterns are tested, and the "champions" identified: the twill pattern with stiffer LCE yarn that shows the greatest blocking force of 1-2 N cm-1 , and the weft rib pattern with over 10% reversible actuation strain on repeated heating cycles. Reversible 3D shape changes of active fabric utilize the circular weaving patterns that lead to cone shapes upon heating. The seamless combination of active LCE yarns into the rich portfolio of existing passive yarns can be transformative in creating new stimuli-responsive actuating textiles.

Potato virus A particles - A versatile material for self-assembled nanopatterned surfaces.

Potato virus A (PVA) is a plant-infecting RNA virus that produces flexible particles with a high aspect ratio. PVA has been investigated extensively for its infection biology, however, its potential to serve as a nanopatterning platform remains unexplored. Here, we study the liquid crystal and interfacial self-assembly behavior of PVA particles. Furthermore, we generate nanopatterned surfaces using self-assembled PVA particles through three different coating techniques: drop-casting, drop-top deposition and flow-coating. The liquid crystal phase of PVA solution visualized by polarized optical microscopy revealed a chiral nematic phase in water, while in pH 8 buffer it produced a nematic phase. This allowed us to produce thin films with either randomly or anisotropically oriented cylindrical nanopatterns using drop-top and flow-coating methods. Overall, this study explores the self-assembly process of PVA in different conditions, establishing a starting point for PVA self-assembly research and contributing a virus-assisted fabrication technique for nanopatterned surfaces.

Ultra-long silver nanowires prepared via hydrothermal synthesis enable efficient transparent heaters.

Ultra-long silver nanowires (AgNWs) with an aspect ratio of >2000 were prepared by the hydrothermal synthesis method. The influence of reaction time (4-32 h), reaction temperature (150-180 °C), polyvinylpyrrolidone (PVP) molecular weight (10 000-1 300 000 g mol-1), PVP concentration (50-125 mM), glucose concentration (5.6-22.4 mM) and CuCl2 concentration (2-20 µM) on the AgNW length was investigated systematically. The optimum conditions provided nanowires with an average diameter of 207 nm, an average length of 234 µm and a maximum length of 397 µm. Finally, a AgNW electrode was prepared on a glass substrate and used in transparent heater application. The transparent heater enabled outstanding heat-generating properties, reaching >200 °C within 70 s with an applied voltage of 5 V. Our results demonstrate how increasing the aspect ratio of ultra-long AgNWs is beneficial for both optical and electronic applications in terms of increased transmission and a more efficient Joule effect in the heater application. In addition, our results show that AgNWs with different lengths can be simply obtained by tuning synthesis parameters.

Design of experiments to investigate multi-additive cellulose nanocrystal films.

Cellulose nanocrystal (CNC) suspensions can self-assemble into chiral nematic films upon the slow evaporation of water. These films are brittle, as indicated by their fracturing instead of plastically deforming once they are fully elastically deformed. This aspect can be mediated to some extent by plasticizing additives, such as glucose and glycerol, however, few reports consider more than one additive at a time or address the influence of additive content on the homogeneity of the self-assembled structure. In this work, design of experiments (DoE) was used to empirically model complex film compositions, attempting to relate additive concentrations in dilute suspension to film properties, and to understand whether outcome specific predictions are possible using this approach. We demonstrate that DoE can be used to predict film properties in multi-additive systems, without consideration given to the different phenomena that occur along the drying process or to the nature of the additives. Additionally, a homogeneity metric is introduced in relation to chiral nematic organization in CNC films, with most of the additive-containing compositions in this work found to reduce the homogeneity of the self-assembly relative to pure CNC films.

Perspective about Cellulose-Based Pressure and Strain Sensors for Human Motion Detection.

High-performance wearable sensors, especially resistive pressure and strain sensors, have shown to be promising approaches for the next generation of health monitoring. Besides being skin-friendly and biocompatible, the required features for such types of sensors are lightweight, flexible, and stretchable. Cellulose-based materials in their different forms, such as air-porous materials and hydrogels, can have advantageous properties to these sensors. For example, cellulosic sensors can present superior mechanical properties which lead to improved sensor performance. Here, recent advances in cellulose-based pressure and strain sensors for human motion detection are reviewed. The methodologies and materials for obtaining such devices and the highlights of pressure and strain sensor features are also described. Finally, the feasibility and the prospects of the field are discussed.

Tuning the Porosity, Water Interaction, and Redispersion of Nanocellulose Hydrogels by Osmotic Dehydration.

Osmotic dehydration (OD) was introduced as a method to reproducibly tune the water content and porosity of cellulose nanofiber (CNF) hydrogels. The hierarchical porosity was followed by electron microscopy (pores with a >100 µm diameter) and thermoporosimetry (mesopores), together with mechanical testing, in hydrogels with solid contents ranging from 0.7 to 12 wt %. Furthermore, a reciprocal correlation between proton conductivity and the ratio of water bound to the nanocellulose network was established, suggesting the potential of these systems toward tunable energy materials.

Plant-Based Structures as an Opportunity to Engineer Optical Functions in Next-Generation Light Management.

This review addresses the reconstruction of structural plant components (cellulose, lignin, and hemicelluloses) into materials displaying advanced optical properties. The strategies to isolate the main building blocks are discussed, and the effects of fibrillation, fibril alignment, densification, self-assembly, surface-patterning, and compositing are presented considering their role in engineering optical performance. Then, key elements that enable lignocellulosic to be translated into materials that present optical functionality, such as transparency, haze, reflectance, UV-blocking, luminescence, and structural colors, are described. Mapping the optical landscape that is accessible from lignocellulosics is shown as an essential step toward their utilization in smart devices. Advanced materials built from sustainable resources, including those obtained from industrial or agricultural side streams, demonstrate enormous promise in optoelectronics due to their potentially lower cost, while meeting or even exceeding current demands in performance. The requirements are summarized for the production and application of plant-based optically functional materials in different smart material applications and the review is concluded with a perspective about this active field of knowledge.

Micro- and nanocelluloses from non-wood waste sources; processes and use in industrial applications.

In addition to renewability and abundance, nanocellulose materials have tremendous (and variable) properties for different applications, ranging from bulk applications, such as paper and packaging reinforcement, to emerging high added-value applications, such as substrates for optoelectronics. Lignocellulosic biomass from agricultural and industrial waste sources is readily available and shows great promise as an inexpensive and sustainable raw material for nanocellulose production. However, the understanding of the potential of using non-wood based biowaste sources is not established and systematic comparisons of versatile agricultural and industrial waste sources can elucidate this complex topic. Here we present an overview of the most studied and most promising sources from agro-industrial waste, the processes to convert them into nanocellulose, some of the established and emerging applications, and discuss the advancements that are still needed for large-scale production. Sugarcane bagasse and oil palm empty fruit bunch have been the most researched waste-based sources for nanocellulose production and demonstrate the most promise due to availability and access. Industrial sources seem to have advantages over agricultural sources in collectability and ease of access. This work gives insight on the potential and the challenges of nanocellulose production from waste sources and discusses how the criteria set for nanocellulose materials in different applications can be met, thus opening new routes for circular economy.

Molecular-Level Photo-Orientation Insights into Macroscopic Photo-Induced Motion in Azobenzene-Containing Polymer Complexes.

As part of continuing efforts to deepen the understanding of photo-induced mass transport in azo-containing polymers, we compared the diffraction efficiency (DE) during surface-relief grating (SRG) inscription, photo-induced molecular orientation (), and thermal stability in two sets of supramolecular azopolymer complexes, namely, hydrogen-bonded (H-bonded) and ionically bonded (i-bonded) complexes, both as a function of the polymer degree of polymerization (DP). To that end, poly(4-vinylpyridine) (P4VP) polymers with DPs of 41, 480, and 1900 were H-bonded at an equimolar ratio with 4-hydroxy-4'-dimethylaminoazobenzene (azoOH), and the fully quaternized derivatives of the three P4VPs (P4VPMe) were i-bonded via ion exchange to sodium 4-[(4-dimethylamino)-phenylazo]benzene sulfonate (azoSO3), also known as methyl orange, where the OH functionality of azoOH is replaced by a sulfonate group. The i-bonded complexes show much better DE performances and levels than those of H-bonded complexes, which we relate to the liquid crystal structure of the former complexes. Fitting the curves by a biexponential equation leads to two parameters associated with a fast trans-cis or angular hole burning (AHB) process and a slow angular redistribution (AR) process of the azo, respectively. It is found that AHB is predominant in the H-bonded complexes, whereas the AR contribution is much greater in the i-bonded complexes, assuring their superior SRG efficiency that is enabled by the anisotropic free volume created mainly by the AR process. In each set of complexes, the SRG efficiency is much better for the lowest DP complex, while the AR contribution is constant (and low) for the H-bonded complexes and increases roughly linearly with the decrease in DP for the i-bonded complexes. The latter difference might be related to the presence of entanglements in the complexes with DPs 480 and 1900, which slow down the macroscopic movement during SRG inscription but not the molecular-scale movement in photo-orientation.

Multiscale Hierarchical Surface Patterns by Coupling Optical Patterning and Thermal Shrinkage.

Herein, a simple hierarchical surface patterning method is presented by effectively combining buckling instability and azopolymer-based surface relief grating inscription. In this technique, submicron patterns are achieved using azopolymers, whereas the microscale patterns are fabricated by subsequent thermal shrinkage. The wetting characterization of various topographically patterned surfaces confirms that the method permits tuning of contact angles and choosing between isotropic and anisotropic wetting. Altogether, this method allows efficient fabrication of hierarchical surfaces over several length scales in relatively large areas, overcoming some limitations of fabricating multiscale roughness in lithography and also methods of creating merely random patterns, such as black silicon processing or wet etching of metals. The demonstrated fine-tuning of the surface patterns may be useful in optimizing surface-related material properties, such as wetting and adhesion, producing substrates that are of potential interest in mechanobiology and tissue engineering.

Understanding nanodomain morphology formation in dip-coated PS-b-PEO thin films.

Block copolymer (BCP) thin films prepared by dip-coating are increasingly investigated, owing to the many promising application areas, the facility, and the industrial scalability of this technique. Yet, the effect of different dip-coating parameters on BCP nanostructure formation is still underdeveloped and the results of previous literature are limited to a few block copolymers. Here, we study the effect of the withdrawal rate and solvent selectivity on the morphology evolution of dip-coated polystyrene-b-poly(ethylene oxide) thin films by applying a wide range of dip-coating speeds and altering the volume ratio of the tetrahydrofuran-water solvent system. The dip-coated films were characterized using atomic force microscopy and ellipsometry. The nanodomain morphology, its feature sizes, its spanning, and the degree of ordering were investigated with regard to different dip-coating parameters. Notably, we have obtained a hexagonally packed BCP pattern with long-range order without the need for post-annealing processes. Overall, a solid understanding of the parameters affecting the formed surface patterns and their interplay was attained and explained, extending the knowledge of this field to more materials.

Cellulose Nanocrystal Aerogels as Electrolyte Scaffolds for Glass and Plastic Dye-Sensitized Solar Cells.

The fabrication, thickness, and structure of aerogel films composed of covalently cross-linked cellulose nanocrystals (CNCs) and poly(oligoethylene glycol methacrylate) (POEGMA) were optimized for use as electrolyte absorbers in dye-sensitized solar cells (DSSCs). The aerogel films were cast directly on transparent conducting counter electrode substrates (glass and flexible poly(ethylene terephthalate) plastic) and then used to absorb drop-cast liquid electrolyte, thus providing an alternative method of filling electrolyte in DSSCs. This approach eliminates the use of electrolyte-filling holes, which are a typical pathway of electrolyte leakage, and furthermore enables a homogeneous distribution of electrolyte components within the photoelectrode. Unlike typical in situ electrolyte gelation approaches, the phase inversion method used here results in a highly porous (>99%) electrolyte scaffold with excellent ionic conductivity and interfacial properties. DSSCs prepared with CNC-POEGMA aerogels reached similar power conversion efficiencies as compared to liquid electrolyte devices, indicating that the aerogel does not interfere with the operation of the device. These aerogels retain their structural integrity upon bending, which is critical for their application in flexible devices. Furthermore, the aerogels demonstrate impressive chemical and mechanical stability in typical electrolyte solvents because of their stable covalent cross-linking. Overall, this work demonstrates that the DSSC fabrication process can be simplified and made more easily upscalable by taking advantage of CNCs, being an abundant and sustainable bio-based material.